Journal of Molecular Liquids 256 (2018) 58–66

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

New aspects in the thermochemistry of solid-liquid phase transitions of

organic non-electrolytes
Mikhail I. Yagofarov, Ruslan N. Nagrimanov, Boris N. Solomonov ⁎
Department of Physical Chemistry, Kazan Federal University, Kremlevskaya str. 18, 420008 Kazan, Russia

a r t i c l e i n f o a b s t r a c t

Article history: Thermochemistry of solid-liquid phase transitions plays an important role in solidification studies of polymers,
Received 31 October 2017 metals, inorganic salts, and low-molecular organic compounds. Enthalpy of fusion is a source of information
Received in revised form 28 December 2017 about intermolecular interactions in materials, crystallinity, mixtures phase diagrams shape, heat transfer in
Accepted 20 January 2018
the solidification interval.
Available online xxxx
The present paper is devoted to relationship between the fusion enthalpies of aromatic compounds at the melt-
Keywords:
ing temperature and the solution enthalpies in benzene at 298.15 K. Sublimation and vaporization thermochem-
Fusion enthalpy istry are used as an additional source of information about the latter relationship. Depending on the magnitude of
Solution enthalpy deviation between the solution enthalpies in benzene at 298.15 K and fusion enthalpies at the melting temper-
Sublimation enthalpy ature, aromatic compounds are conventionally divided into three groups. For a large number of aromatic com-
Organic non-electrolytes pounds not capable of self-association the equality between the fusion enthalpies at the melting temperature
and the solution enthalpies in benzene at 298.15 K is established. For self-associated aromatic compounds the so-
lution enthalpy in benzene at 298.15 K exceeds the fusion enthalpy at the melting temperature, and insertion of a
substituent not forming inter- and intramolecular hydrogen bonds does not affect the difference between the so-
lution and fusion enthalpies. The enthalpies of solution in benzene at 298.15 K of several aromatic compounds
not capable of self-association appear to be visibly less than the fusion enthalpies at the melting temperature.
The reasons of different relationships between the fusion and solution enthalpies are analyzed using Kirchhoff's
law for the fusion enthalpy.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction
Calorimetry has been used extensively in materials science since the
19th century. Nowadays it is necessary in both fundamental and applied
investigations of metals and alloys, polymers, composites, inorganic
salts, ceramics and glasses, organic low-molecular compounds.
One of the key quantities obtained using calorimetry is the enthalpy
of fusion. The fusion enthalpies of pure compounds are commonly used
for prediction and analysis of solid-liquid equilibrium phase diagrams
shapes, including studies of mixtures of metals [1], inorganic salts [2],
organic compounds [3,4]. In the case of low-molecular organic com-
pounds, especially biologically active substances, the solubilities in
water, common organic solvents, and mixtures are frequently predicted
with the use of the fusion enthalpies [5–11]. Calorimetric methods in-
volving latent heat of fusion measurement find application in investiga-
tion on polymorphic modifications [12–14]. The fusion enthalpy value
is important for the modeling of heat transfer during solidification
⁎ Corresponding author.
E-mail address: boris.solomonov@kpfu.ru (B.N. Solomonov).
process in metals [15–19] and polymers [20]. One of the widest applica-
tions of fusion enthalpy measurements is a determination of a degree of
crystallinity in semi-crystalline polymers [21–29] and blends, e. g. poly
(3-hydroxybutyrate) – poly(ethylene glycol) [30], hydroxypropyl cellu-
lose – polyvinyl alcohol [27], hydroxypropyl lignin – polyvinyl alcohol
[31].
Many techniques exist which allow determining fusion enthalpy at
the melting temperature (ΔlcrHAi(Tm)) with varying accuracy: dynamic
methods, such as differential scanning calorimetry [32] and its modifi-
cations (temperature modulated differential scanning calorimetry
[33], fast scanning calorimetry [29], etc. [34]); adiabatic calorimetry
[34–37]; mixtures phase-change calorimetry (e.g. ice calorimeter
[38]); drop calorimetry [39,40]; levitation techniques [41]; freezing
point method [42]; derivation from sublimation and vaporization en-
thalpies [43]. Several reviews are available on calorimetric methods of
measurement of solid-liquid phase change enthalpies [34,44–46].
Apart from correct device handling during an experiment, measure-
ment accuracy strongly depends on the quality of specimen preparation
and its thermal stability. Presence of impurities, high-temperature
chemical processes in the sample can drastically affect fusion enthalpy
magnitude.

https://doi.org/10.1016/j.molliq.2018.01.114
0167-7322/© 2018 Elsevier B.V. All rights reserved.
 M.I. Yagofarov et al. / Journal of Molecular Liquids 256 (2018) 58–66
Accurate measurement of the fusion enthalpy of a pure substance is
usually possible only at the equilibrium melting temperature. However,
it is often necessary to know the difference between the enthalpies of
the solid and liquid at the temperature distinct from the melting
point. This difference is frequently supposed to be indistinguishable
from the fusion enthalpy at the melting temperature [47–50], at least
for small temperature intervals. However, neglect of fusion enthalpy
temperature dependence may affect an accuracy of polymers crystallin-
ity degree determination [24,25], correctness of prediction of solid frac-
tion in the melt during solidification [1]. Significance of the fusion
enthalpy temperature dependence in solubility prediction was inten-
sively discussed in the last decades [49,51–53]. Several empirical ap-
proaches were developed to estimate this dependence [54–56].
Ogawa et al. [57] stated that the solution enthalpies of solid aromatic
hydrocarbons (naphthalene, anthracene, naphthacene, and chrysene)
in a number of organic solvents (cyclohexane, heptane, 1,4-dioxane,
benzene, and chloroform) (ΔsolnHAi/S(cr, 298.15 K)) change similarly
with ΔlcrHAi(Tm). Briard et al. [58] pointed out that ΔlcrHAi(Tm) of long-
chain alkanes are nearly equal to ΔsolnHAi/S(cr,298.15 K) in heptane at
298.15 K.
Novel view on melting thermochemistry of organic compounds has
been recently developed in our laboratory based on solution calorime-
try [59–66]. In the present paper we generalize the results of the
works [57–64] devoted to relationships between the solution enthalpy
at 298.15 K and the fusion enthalpy at the melting temperature. This
generalization is aimed at establishment of the reasons of agreement
and disagreement between two experimentally measured values (ΔlcrH-
Ai
(Tm)and ΔsolnHAi/S (cr, 298.15 K)).
2. Methodology
The molar enthalpy of solution (ΔsolnHAi/S) is the enthalpy change
when 1 mol of a solute Ai dissolves in a sufficient amount of a solvent
S to give a solution of infinite dilution. The solution and fusion en-
thalpies of a solid compound Ai in a solvent S at 298.15 K are related
by the following equation:
Δsoln HAi =S ðcr; 298:15 KÞ ¼ Δlcr HAi ð298:15 KÞ þ Δsoln H Ai =S ðl; 298:15 KÞð1Þ
where ΔlcrHAi(298.15 K) is the fusion enthalpy of Ai at 298 K. ΔlcrHAi
(298.15 K) and ΔsolnHAi/S (l, 298.15 K) are hypothetical values for a com-
pound Ai that is solid under standard conditions.
According to Kirchhoff's law, ΔlcrHAi(298.15 K) is related to ΔlcrHAi
(Tm) as follows:
X The mean solution enthalpy value derived from ΔsolnHAi/C6H6(l,
Δlcr H Ai ð298:15 KÞ ¼ Δlcr HAi ðT m Þ þ Δtrns HAi ðT trns Þ
Z h
298:15
i association [65,70,72,82,83,86] is 0.8 ± 0.7 kJ mol−1. At the same
þ C Ap i ðl; T Þ−C Ap i ðcr; T Þ dT
Tm
where ∑ΔtrnsHAi(Ttrns) is a sum of all solid-solid phase transitions en-
thalpies occurring from 298.15 K to Tm; CAp i(l, T) is the molar heat capac-
ity of the compound Ai in the liquid phase at the temperature T; CAp i(cr, T)
is that of Ai in the solid phase. CAp i(l, T) below Tm is generally unknown.
Therefore, except for compounds which may be deeply supercooled,
one cannot strictly determine the fusion enthalpy below Tm using
Kirchhoff's law.
Combining Eqs. (1) and (2), we obtain Eq. (3):
Δsoln HAi =S ðcr; 298:15 KÞ−Δsoln H Ai =S ðl; 298:15 KÞ ¼
X Z h
298:15
i Approximate equality of the solution enthalpies in benzene and the
¼ Δlcr HAi ðT m Þ þ Δtrns H Ai ðT trns Þ þ C Ap i ðl; T Þ−C Ap i ðcr; T Þ dT
Tm
Eq. (3) connects the solution enthalpies of a compound Ai in the
solid and hypothetical liquid states, the fusion enthalpy at the melting
59
temperature and its thermal adjustment to 298.15 K. The relationship
between ΔsolnHAi/S(cr,298.15 K) and ΔlcrHAi(Tm) depends on the values
P R 298:15
of ΔsolnHAi/S(l, 298.15 K) and Δtrns H Ai ðT trns Þ þ T m ½C Ap i ðl; TÞ−C Ap i ðcr;
TÞdT. We studied this relationship for more than 200 aromatic com-
pounds and observed that for the majority of the compounds not capa-
ble of self-association the solution enthalpies in benzene (ΔsolnHAi/C6H6
(cr, 298.15 K)) and ΔlcrHAi(Tm)) are nearly equal [61,62]. ΔsolnHAi/C6H6
(cr, 298.15 K) of self-associated aromatic compounds (e.g., substituted
phenols) were observed to be notably larger than the ΔlcrHAi(Tm) values
[63]. In contrast, for several aromatic hydrocarbons, heterocycles and
their derivatives not capable of self-association the ΔsolnHAi/C6H6(cr,
298.15 K) values were significantly less than ΔlcrHAi(Tm) [65,66]. Further
in the article each type of deviation (zero, positive or negative) between
ΔsolnHAi/C6H6(cr, 298.15 K) and ΔlcrHAi(Tm) is analyzed in details.
3. Results and discussion
3.1. Approximate equality between the fusion and solution enthalpies in
benzene of aromatic compounds not capable of self-association
The values of ΔsolnHAi/S(cr, 298.15 K) and ΔlcrHAi(Tm) can be approxi-
P
mately equal if the contributions by ΔsolnHAi/S(l,298.15 K) and Δtrns
R 298:15
H Ai ðT trns Þ þ T m ½C Ap i ðl; TÞ−C Ap i ðcr; TÞdT have the same sign and com-
pensate each other or if both contributions are small.
Let's consider the case when ΔsolnHAi/S(l,298.15 K) in Eq. (3) is zero.
Thence, it can be re-written in the following form:
X
Δsoln H Ai =S ðcr; 298:15 KÞ−Δlcr H Ai ðT m Þ− Δtrns HAi ðT trns Þ ¼
Z h
298:15
i ð4Þ
¼ C Ap i ðl; T Þ−C Ap i ðcr; T Þ dT
Tm
ΔsolnHAi/S(cr, 298.15 K), ∑ΔtrnsHAi(Ttrns) and ΔlcrHAi(Tm) are mea-
sured directly. The difference between them is equal to the thermal ad-
justment of the fusion enthalpy to 298.15 K
R 298:15 Ai Ai
Tm ½C p ðl; TÞ−C p ðcr; TÞdT.
A liquid compound Ai can be dissolved in a solvent S with small heat
effect when Ai and S have similar chemical structures (“like dissolves
like” principle). A good example is dissolution of liquid aromatic com-
pounds not capable of self-association in benzene. The solution enthalpies
at 298.15 K of a number of liquid aromatic compounds in benzene, cyclo-
hexane, tetrachloromethane, acetonitrile are provided in Table 1.
298.15 K) of 40 liquid aromatic compounds not capable of self-
ð2Þ time, the solution enthalpies in other common solvents are notably
larger.
Thus, Eq. (4) can be applied for solid aromatic hydrocarbons and
their derivatives not capable of self-association with the use of benzene
as solvent, since the solution enthalpies of these compounds in hypo-
thetical liquid state in benzene (ΔsolnHAi/C6H6(l, 298.15 K)) should be
also close to zero. For a large number of aromatic hydrocarbons and
their derivatives we observed that their ΔsolnHAi/C6H6(cr, 298.15
K) values are nearly equal to a sum of ΔlcrHAi(Tm) and ∑ΔtrnsHAi(Ttrns)
[59]:
X
Δsoln HAi =C6 H6 ðcr; 298:15 KÞ ≈ Δlcr H Ai ðT m Þ þ Δtrns H Ai ðT trns Þ ð5Þ
ð3Þ
fusion enthalpies was proved for a wide range of aromatic and
heteroaromatic compounds as follows.
The molar enthalpy of solvation (ΔsolvHAi/S) is the enthalpy change
when 1 mol of gaseous molecules of a solute Ai dissolves in a solvent
to give a solution of infinite dilution. The molar enthalpy of
60 M.I. Yagofarov et al. / Journal of Molecular Liquids 256 (2018) 58–66

Table 1
Solution enthalpies of aromatic compounds (kJ mol−1) in benzene, acetonitrile, cyclohexane, and tetrachloromethane at 298.15 K.

Solute Solvent

C6H6 CH3CN C6H12 CCl4

Benzene 0 2.59 [67] 3.19 [68] 0.63 [69]

Toluene 0.28 ± 0.01 [70] 3.13 [71] 2.94 [68] – 0.13 [72]
tert-Butylbenzene 0.67 ± 0.02 [70] 4.69 ± 0.06 [70] 2.18 [73] – 0.33 [74]
fluorobenzene 0.08 [75] 1.55 [69] 4.60 [75] 1.09 [76]
Chlorobenzene 0.13 [75] 2.76 [69] 3.77 [75] 0.63 [76]
Bromobenzene 0.21 [75] 3.14 [69] 4.48 [75] 0.84 [69]
Methyl benzoate 0.37 ± 0.05[70] 2.3 ± 0.1 [70] 2.3 ± 0.1 [70]
Benzonitrile 0.54 ± 0.08 [70] 1.38 ± 0.07 [70] 4.21 ± 0.06 [70]
Anisole 0.21 [72] 1.96 ± 0.05 [70] 7.20 [77] 1.55 [76]
Benzaldehyde 0.90 [78] 1.51 [78] 3.35 [79]
Acetophenone 1.51 [75] 1.72 ± 0.07 [70] 10.07 [80] 3.31 [76]
1,6-Dimethylnaphthalene 1.46 ± 0.02 [65] 5.98 ± 0.04 [81]
1-Methylnaphthalene 0.78 ± 0.03 [65] 5.1 ± 0.2 [81]
Pyridine 0.04 [82] 1.67 ± 0.01 [70] 8.20 [82] 1.30 [82]
Furan 0.35 ± 0.1 [83] 4.8 [84] 1.07 [85]

vaporization/sublimation (Δgcr(l)HAi(298.15K)) is related to the en-
thalpies of solvation and solution as follows:
ΔgcrðlÞ H Ai ð298:15 KÞ ¼ Δsoln H Ai =S ð298:15 KÞ−Δsolv HAi =S ð298:15 KÞ
Substituting ΔlcrHAi(Tm) + ∑ΔtrnsHAi(Ttrns) instead of ΔsolnHAi/C6H6
(cr, 298.15 K) into Eq. (6) and calculating ΔsolvHAi/C6H6(298.15 K), it is
possible to obtain ΔgcrHAi(298.15 K). One can compare the latter value
with the reference data obtained using conventional methods. In our
opinion, agreement between the calculated and literature sublimation
enthalpies values indirectly evidences approximate equality of the
ΔsolnHAi/C6H6(cr, 298.15 K) and ΔlcrHAi(Tm)+∑ΔtrnsHAi(Ttrns) values.
Earlier [70] we proposed a solvation enthalpy group-additivity
scheme for substituted aromatic hydrocarbons. According to this
scheme, the solvation enthalpy of an arene derivative Ar(Xi)n in a sol-
vent S (ΔsolvHAr(Xi)n/S) can be calculated from the solvation enthalpy of
the unsubstituted arene ArH (ΔsolvHArH/S) and the contributions into
solvation enthalpy of the substituents Xi (ΔsolvHXi→H/S):
Δsolv HArðXi Þn =S ¼ Δsolv H ArH=S þ n  Δsolv H Xi →H=S
In its turn, ΔsolvHXi→H/S is calculated from the solvation enthalpies of
monosubstituted benzene PhXi (ΔsolvHPhXi/S) and benzene (ΔsolvHPhH/S):
plot between calculated and literature ΔgcrHAi(298.15 K) values is
shown in Fig. 1.
The average of absolute deviations between the literature and calcu-
ð6Þ lated sublimation enthalpies values is equal to 1.7 kJ mol−1. It reflects
robustness of sublimation enthalpy calculation based on solvation en-
thalpy group-additivity scheme and fusion enthalpy. The average of de-
viations between literature and calculated values is – 0.1 kJ mol−1. It
indirectly supports the correctness of Eq. (5).
Approximate equality of the fusion enthalpies at the melting en-
thalpies and the solution enthalpies of aromatic compounds not capable
of self-association in benzene, as well as good agreement between the
sublimation enthalpies taken from literature and derived from the fu-
sion enthalpies at the melting temperature lead to a conclusion that
the fusion enthalpy weakly depends on temperature. At least, the tem-
perature dependence should be weaker than it is predicted by Chickos
et al. scheme [54] for some PAHs [108]. For example, ΔlcrHAi(298.15 K)
of pyrene provided in Ref. [108] is equal to 10.2 ± 2.3 kJ mol−1. At the
same time, the solution and fusion enthalpies of pyrene differ less:
ΔsolnHAi/C6H6(298.15 K) = 16.3 kJ mol−1 [86] and ΔlcrHAi(Tm) =
ð7Þ 17.36 kJ mol−1 [108], indicating that the fusion enthalpy of pyrene at
298.15 K is close to that at the melting temperature.
3.2. Self-associated aromatic compounds: searches of regularities

Δsolv HXi →H=S ¼ Δsolv H PhXi =S −Δsolv HC6 H6 =S ð8Þ ΔsolnHAi/C6H6(l, 298.15 K) does not remain zero for aromatic com-
pounds capable of self-association due mainly to intermolecular hydro-
Farther we extended group-additivity to polyaromatic [59] and gen bonding. Liquid self-associated aromatic compounds dissolve in
heteroaromatic [83] compounds. Using solvation enthalpy group-
additivity scheme and high-precision solution calorimetry, we calcu- Table 2
lated Δgcr(l)HAi(298.15K) of more than 150 aromatic compounds Comparison between the ΔsolvHAi/C6H6(298.15 K) and Δgl HAi (298.15 K) values of aromatic
[59,61,63,83,87–96]. Agreement of the calculated values with the refer- derivatives.
ence data obtained by conventional measurement methods was within Compound Δgl HAia ΔsolvHAi/C6H6b
the limits of 2–3 kJ mol−1. kJ mol−1 kJ mol−1
For aromatic compounds not capable of self-association, ΔsolvHAi/ Methyl 4-fluorobenzoate 56.0 ± 0.1 [97] 54.8
C H g Ai
6 6(298.15 K) should be close to the vaporization enthalpies (Δl H 1,3,5-Trimethylbenzene 47.5 ± 2.1 [98] 45.3
Ai/C H
(298.15 K)), because ΔsolnH 6 6(l, 298.15 K) is small (see Table 1). In 2-Methylquinoline 62.6 ± 0.1 [99] 62.8
Table 2 comparison is provided between the experimental Δgl HAi Bromopentafluorobenzene 43.1 ± 0.2 [100] 41.5
1,4-Dichlorobenzene 47.8 [101] 47.0
(298.15 K) values and ΔsolvHAi/C6H6(298.15 K) calculated according to
1,2,3,4-Tetrachlorobenzene 60.1 [102] 59.2
group-additivity scheme. 1-Bromo-4-chlorobenzene 52.3 ± 0.6 [103] 49.6
Average difference between Δgl HAi(298.15 K) and ΔsolvHAi/C6H6 1,4-Diiodobenzene 59.9 [104] 61.4
(298.15 K) in Table 2 is 0.9 ± 1.2 kJ mol−1, being close to the average 3-Chloronitrobenzene 60.2 ± 0.2 [105] 58.8
3,4-Dichloronitrobenzene 65.2 ± 0.2 [105] 64.9
of ΔsolnHAi/C6H6(l,298.15 K) of 40 liquid aromatic compounds mentioned
2,2′,3,4,4′,5′–Hexachlorobiphenyl 99.9 [106] 100.0
above (0.8 ± 0.7 kJ mol−1). The average of absolute deviations between Dimethyl isophthalate 77.2 ± 0.8 [107] 75.6
the literature and calculated values is 1.2 kJ mol−1. a
The vaporization enthalpies values at 298.15 K. For the compounds studied at elevated
Using the fusion enthalpies at the melting temperature and solva- temperatures, Δgl HAi were adjusted to 298.15 K using Chickos et al. scheme [54].
tion enthalpy group-additivity scheme, we calculated the sublimation b
The solvation enthalpies at 298.15 K calculated according to group-additivity scheme
enthalpies of 15 PAHs [59] and 80 their derivatives [60]. Deviation [70].
 M.I. Yagofarov et al. / Journal of Molecular Liquids 256 (2018) 58–66
Fig. 1. Deviation plot between calculated and recommended sublimation enthalpies
values for PAHs and their derivatives. 1 – 1,4-dichlorobenzene; 2 – 1,2,3-trichlorobenzene;
3 – 1,3,5-trichlorobenzene; 4 – 1,2,3,5-tetrachlorobenzene; 5 – 1,2,3,4-tetrachlorobenzene;
6 – 1,2,4,5-tetrachlorobenzene; 7 – pentachlorobenzene; 8 – hexachlorobenzene; 9 – 4-
chlorobiphenyl; 10 – 2-chloronaphthalene; 11 – 9-chloroanthracene; 12 – 9,10-
dichloroanthracene; 13 – 9-chlorophenanthrene; 14 – 1-chloropyrene; 15 – 1,4-
dibromobenzene; 16 – 2-bromonaphthalene; 17 – 1,4-dibromonaphthalene; 18 – 4-
bromobiphenyl; 19 – 4,4-dibromobiphenyl; 20 – 9-bromoanthracene; 21 – 9,10-
dibromoanthracene; 22 – 1,5-dibromoanthracene; 23 – 9-bromophehanthrene; 24 – 7-
bromobenz[a]anthracene; 25 – 1,3-diiodobenzene; 26 – 1,4-diiodobenzene; 27 – 1-
bromo-4-chlorobenzene; 28 – 1-bromo-4-iodobenzene; 29 – 1,2-dinitrobenzene; 30 –
1,3-dinitrobenzene; 31 – 1,4-dinitrobenzene; 32 – 1,3,5-trinitrobenzene; 33 – 1-
nitronaphthalene; 34 – 9-nitroanthracene; 35 – 1-nitropyrene; 36 – 1,2-
dicyanobenzene; 37 – dimethyl isophthalate; 38 – dimethyl terephthalate; 39 –
trimethyl 1,3,5-benzenetricarboxylate; 40 – 1,4-dimethoxybenzene; 41 – 1,4-
dimethylbenzene; 42 – 1,4-di-tert-butylbenzene; 43 – 3,5-di-tert-butyltoluene; 44 –
1,3,5-tri-tert-butylbenzene; 45 – 4-methylbiphenyl; 46 – 4-tert-butylbiphenyl; 47 – 4,4-
di-tert-butylbiphenyl; 48 – 1,8-dimethylnaphthalene; 49 – 2,3-dimethylnaphthalene;
50 – 2,6-dimethylnaphthalene; 51 – 2,7-dimethylnaphthalene; 52 – 4-bromotoluene;
53 – 4-iodotoluene; 54 – 1-chloro-2-nitrobenzene; 55 – 1-chloro-3-nitrobenzene; 56 –
1-chloro-4-nitrobenzene; 57 – 1,2-dichloro-4-nitrobenzene; 58 – 4-nitrotoluene; 59 –
2,4-dinitrotoluene; 60 – 2,6-dinitrotoluene; 61 – 2,4,6-trinitrotoluene; 62 – 3-methyl-
2,4,6-trinitrotoluene; 63 – 2-chlorobenzonitrile; 64 – 3-chlorobenzonitrile; 65 – 4-
chlorobenzonitrile; 66 – 3-fluorobenzonitrile; 67 – 4-fluorobenzonitrile; 68 – methyl 4-
fluorobenzoate; 69 – methyl 4-chlorobenzoate; 70 – methyl 4-bromobenzoate; 71 –
methyl 4-iodobenzoate; 72 – methyl 4-methylbenzoate; 73 – methyl 4-
methoxybenzoate; 74 – methyl 4-(dimethylamino)benzoate; 75 – methyl nicotinate;
76 – methyl isonicotinate; 77 – diphenylacetylene; 78 – 1-pyrenecarboxaldehyde; 79 –
acenaphthylene; 80 – biphenylene; 81 – naphthacene; 82 – triphenylene; 83 –
corannulene; 84 – perylene; 85 – benzo[a]pyrene; 86 – benzo[e]pyrene; 87 – benzo[k]
fluoranthene; 88 – benzo[ghi]perylene; 89 – benzo[b]triphenylene; 90 – picene; 91 –
benzo[b]chrysene; 92 – coronene; 93 – 1,2:4,5-dibenzopyrene; 94 – 2-
bromoanthracene; 95 – 9,10-dibromophenanthrene.
benzene with a notable endothermic effect, e.g. ΔsolnHAi/C6H6(l,
298.15 K) of 3-fluorophenol is 7.5 kJ mol−1 [109], that of aniline is
4.9 kJ mol−1 [64]. Rupture of strong hydrogen bonds in a liquid phase
of a self-associated compound requires more energy than evolved due
to the formation of a weak hydrogen bond with benzene, while disper-
sion interactions energy stays nearly the same. ΔsolnHAi/C6H6(l, 298.15 K)
cannot be neglected in Eq. (3) for self-associated aromatic compounds.
We have observed for non-self-associated aromatic compounds that
R 298:15
often the T m ½C Ap i ðl; TÞ−C Ap i ðcr; TÞdT value is insignificant. It is reason-
able to assume that it can be right for some self-associated aromatic
compounds too. The following relationship should be satisfied for such
compounds in the absence of solid-solid phase transitions between
298.15 K and Tm:
Δsoln HPhY=C6 H6 ðcr; 298:15 KÞ ¼ Δlcr H PhY ðT m Þ
þ Δsoln H PhY=C6 H6 ðl; 298:15 KÞ
61
The data available to us allows stating that the solution enthalpies of
liquid self-associated aromatic compounds (anilines, phenols) in ben-
zene are influenced weakly by insertion of a substituent which does
not cause self-association and does not form an intramolecular hydro-
gen bond with a self-associating group. This observation was extended
to solid phenols with the help of Eq. (10), according to which ΔsolnH-
PhY/C6H PhY/C6H
6(l, 298.15 K) can be calculated from ΔsolnH 6(cr, 298.15 K)
l PhY
and ΔcrH (Tm). It was shown [61] that the solution enthalpies of
substituted phenols in the hypothetical liquid state (ΔsolnH(Xi)nPhOH/
C H
6 6(l, 298.15 K)) obtained in this way remain constant, regardless the
substituent:
Δsoln HðXi Þn PhOH=C6 H6 ðl; 298:15 KÞ ¼ Δsoln H PhOH=C6 H6 ðl; 298:15 KÞ ð10Þ
This result can be further used for establishment of the relationship
between ΔlcrHAi(Tm) and ΔgcrHAi(298.15 K) of self-associated aromatic
compounds.
Solvation enthalpy in benzene of self-associated aromatic com-
pound PhY with a group Y causing self-association (ΔsolvHPhY/C6H6
(298.15 K)) can be represented as follows:
Δsolv HPhY=C6 H6 ð298:15 KÞ
¼ Δsoln H PhY=C6 H6 ðcr; 298:15 KÞ−Δgcr HPhY ð298:15 KÞ ð11Þ
Substituting Eq. (9) into Eq. (11), we can obtain a new expression for
ΔsolvHPhY/C6H6(298.15K):
Δsolv H PhY=C6 H6 ð298:15 KÞ ¼ Δlcr HPhY ðT m Þ þ Δsoln H PhY=C6 H6 ðl; 298:15 KÞ−
−Δgcr HPhY ð298:15 KÞ
ð12Þ
On the other hand, solvation enthalpy of PhY containing substituents
Xi not causing self-association (ΔsolvH(Xi)nPhY/C6H6) can be calculated as
follows [70]:
Δsolv HðXi Þn PhY=C6 H6 ¼ Δsolv H PhY=C6 H6 þ n  Δsolv H Xi →H=C6 H6 ð13Þ
Combining Eqs. (12) and (13), we obtain Eq. (14):
Δsolv HðXi Þn PhY=C6 H6 ð298:15 KÞ ¼ Δlcr HPhY ðT m Þ þ Δsoln HPhY=C6 H6 ðl; 298:15 KÞ−
−Δgcr H PhY ð298:15 KÞ−n  Δsolv HXi →H=C6 H6 ð298:15 KÞ
ð14Þ
In the absence of solid-solid transitions from 298.15 K to Tm, we can
write an expression for sublimation enthalpy of (Xi)nPhY (ΔgcrH(Xi)nPhOH
(298.15K)):
Δgcr HðXi Þn PhY ð298:15 KÞ ¼ Δlcr HðXi Þn PhY ðT m Þ þ Δsoln HðXi Þn PhY=C6 H6 ðl; 298:15 KÞ−
−Δlcr HPhY ðT m Þ−Δsoln HPhY=C6 H6 ðl; 298:15KÞ þ Δgcr HPhY ð298:15 KÞ−n  Δsolv HXi →H=C6 H6
ð15Þ
The relation above can be simplified if Eq. (10) is true in general case
for PhY and (Xi)nPhY:
Δgcr H ðXi Þn PhY ð298:15KÞ ¼ Δlcr HðXi Þn PhY ðT m Þ þ Δgcr HPhY ð298:15KÞ−
ð16Þ
−Δlcr HPhY ðTm Þ−n  Δsolv H Xi →H=C6 H6
Eq. (16) can be modified and further applied to self-associated com-
pounds with polyaromatic and heteroaromatic core, as well as to the
compounds with several groups causing self-association, such as resor-
cinol or p-phenylenediamine [61–64].
We used Eq. (16) for calculation of sublimation enthalpies of more
than 80 self-associated aromatic compounds: benzoic acid derivatives
[62], substituted phenols [61], benzamides [63], aromatic amines [64]
ð9Þ and their poly- and heteroaromatic analogues.
62 M.I. Yagofarov et al. / Journal of Molecular Liquids 256 (2018) 58–66
Deviation plot between calculated and average literature values for
aromatic and heteroaromatic carboxylic acids, substituted phenols, aro-
matic and heteroaromatic amides, aromatic amines is provided in Fig. 2.
The average of absolute deviations between the literature and calcu-
lated sublimation enthalpies values is 1.7 kJ mol−1. The average of devi-
ations between the literature and calculated values is 0.2 kJ mol−1.
Thus, Eq. (16) describes sublimation thermochemistry of self-
associated aromatic compounds with a satisfactory accuracy. During
derivation of Eq. (16) two assumptions were made. Firstly, it was sup-
posed that the temperature dependence of the fusion enthalpy is
weak and solution enthalpy of solid self-associated aromatic compound
can be found as a sum of the fusion enthalpy at the melting temperature
and the solution enthalpy of hypothetical liquid (Eq. 9). Secondly, it was
supposed that solution enthalpy of liquid self-associated aromatic com-
pounds is determined mainly by the substituent causing self-association
and is weakly affected by insertion of other substituents if they do not
interact with the latter (Eq. 10). This assumption is supported by the
data on the solution enthalpies of liquid phenols in benzene [61]. In its
turn, the differences between the solution enthalpies of solid phenols
Fig. 2. Deviation plot between calculated and average literature sublimation enthalpies
values for self-associated aromatic and heteroaromatic compounds. 1 – 4-fluorophenol;
2 – 4-chlorophenol; 3 – 3-chlorophenol; 4 – 3,4-dichlorophenol; 5 – 4-bromophenol;
6 – 4-iodophenol; 7 – 2-hydroxytoluene; 8 – 3-hydroxytoluene; 9 – 4-hydroxytoluene;
10 – 2,3-dimethylphenol; 11 – 2,5-dimethylphenol; 12 – 3,4-dimethylphenol; 13 – 3,5-
dimethylphenol; 14 – 2,3,6-trimethylphenol; 15 – 4-iso-propylphenol; 16 – 2-iso-
propyl-5-methylphenol; 17– 3-tert-butylphenol; 18 – 4-tert-butylphenol; 19 – 3-
nitrophenol; 20 – 4-nitrophenol; 21 – 4-chloro-3-nitrophenol; 22 – 3-methyl-4-
nitrophenol; 23 – 4-methoxyphenol; 24 – 4-hydroxyacetophenone; 25 – methyl 4-
hydroxybenzoate; 26 – 1,3-dihydroxybenzene; 27 – 1,4-dihydroxybenzene; 28 – 2-
methyl-1,4-dihydroxybenzene; 29 – 3-fluorobenzamide; 30 – 4-fluorobenzamide; 31 –
2-methylbenzamide; 32 – 3-methylbenzamide; 33 – 4-methylbenzamide; 34 – 3-
methoxybenzamide; 35 – 4-methoxybenzamide; 36 – nicotinamide; 37 –
isonicotinamide; 38 – 3-aminobenzamide; 39 – 4-aminobenzamide; 40 – 4-
hydroxybenzamide; 41 – 3-nitrobenzamide; 42 – 4-nitrobenzamide; 43 – 4-toluidine;
44 – 4-chloroaniline; 45 – 3,4-dichloroaniline; 46 – 4-bromoaniline; 47 – 4-iodoaniline;
48 – 3-nitroaniline; 49 – 4-nitroaniline; 50 – 4-aminoacetophenone; 51 – methyl 3-
aminobenzoate; 52 – methyl 4-aminobenzoate; 53 – 3,5-difluoroaniline; 54 – 3,4,5-
trifluoroaniline; 55 – 1,3-diaminobenzene; 56 – 1,4-diaminobenzene; 57 – 3-
aminophenol; 58 – 4-aminophenol; 59 – 4-aminobenzoic acid; 60 – 1-naphthylamine;
61 – 2-naphthylamine; 62 – 2-fluorobenzoic acid; 63 – 3-fluorobenzoic acid; 64 – 4-
fluorobenzoic acid; 65 – 2-chlorobenzoic acid; 66 – 3-chlorobenzoic acid; 67 – 4-
chlorobenzoic acid; 68 – 2-bromobenzoic acid; 69 – 3-bromobenzoic acid; 70 – 4-
bromobenzoic acid; 71 – 2-iodobenzoic acid; 72 – 3-iodobenzoic acid; 73 – 3,5-
dibromobenzoic acid; 74 – 2-methylbenzoic acid; 75 – 4-methylbenzoic acid; 76 – 3,5-
dimethylbenzoic acid; 77 – 2-methoxybenzoic acid; 78 – 3-methoxybenzoic acid; 79 –
4-methoxybenzoic acid; 80 – 2-nitrobenzoic acid; 81 – 3-nitrobenzoic acid; 82 – 2,4-
dinitrobenzoic acid; 83 – 3,4-dinitrobenzoic acid; 84 – monomethyl isophthalate; 85 –
monomethyl terephthalate; 86 – 1-naphthoic acid; 87 – 2-naphthoic acid; 88 – 2-
furancarboxylic acid; 89 – 3-furancarboxylic acid; 90 – 2-thiophenecarboxylic acid; 91 –
3-thiophenecarboxylic acid; 92 – isophthalic acid; 93 – terephthalic acid; 94 – 2,5-
dibromobenzoic acid; 95 – 4-iodobenzoic acid; 96 – 3-methylbenzoic acid; 97 – 2,3-
dimethylbenzoic acid; 98 – 4-nitrobenzoic acid.
and the fusion enthalpies at the melting temperature are approximately
equal to each other and to the solution enthalpies of liquid phenols. It
supports the validity of Eq. (9). Finally, good agreement between the
sublimation enthalpies calculated according to Eq. (16) and taken
from literature confirms applicability of the above mentioned assump-
tions for the wider range of compounds from different classes. However,
it should be taken into account that in Eq. (16) the fusion enthalpy of
PhY at the melting temperature is subtracted from that of (Xi)nPhY, so
the temperature dependences of the fusion enthalpies may partially
compensate, especially if (Xi)nPhY and PhY have close melting points.
3.3. Solution calorimetry as a source of information about the temperature
dependence of the fusion enthalpy
Occasionally ΔsolnHAi/C6H6(cr, 298.15 K) are notably less than ΔlcrHAi
(Tm) of aromatic compounds not capable of self-association. For exam-
ple, ΔsolnHAi/C6H6(cr, 298.15 K) of anthracene in Table 1 is less than ΔlcrH-
Ai
(Tm) by 4.7 kJ mol−1. According to Eq. (4), this difference corresponds
R 298:15
to T m ½C Ap i ðl; TÞ−C Ap i ðcr; TÞdT.
Some organic compounds may be supercooled, and their CAp i(l, T)
below Tm can be measured. The experimental data on CAp i(l, T) of benzo-
phenone [110] and o-terphenyl [111] show that CAp i(l, T) below Tm can be
fairly represented with the same function of temperature as CAp i(l, T)
above Tm. The temperature dependences of solid and liquid heat capac-
ities of o-terphenyl fitted from numerical data points from [111] are
shown in Fig. 3a.
p-Terphenyl melts at 487 K. It immediately freezes when cooled
below Tm. Heat capacities of solid and liquid p-terphenyl were compre-
hensively studied in [112]; their temperature dependences (solid black
and red curves, respectively) are shown in Fig. 3b. CAp i(l, T) of p-terphenyl
above Tm demonstrates almost linear behavior. To improve fitting qual-
ity, heat capacities of the solids and liquids are also represented as qua-
dratic polynomials [110,113] in the measurements temperature range.
Of course, extrapolation of polynomials for liquids down to 298.15 K
R Tm
using Kirchhoff's law should be performed with a great caution. 298:15 ½
C Ap i ðl; TÞ−C Ap i ðcr; TÞdT for p-terphenyl calculated assuming that CAp i(l, T)
behaves linearly between 298.15 K and Tm (dashed red line) is equal to
7.7 kJ mol−1. If CAp i(l, T) is fitted with quadratic polynomial (dashed
R Tm
green line), then 298:15 ½C Ap i ðl; TÞ−C Ap i ðcr; TÞdT is equal to 12.9 kJ mol−
1
. The higher degree polynomials lead to extremely big thermal adjust-
ment values, either positive or negative. ΔsolnHAi/C6H6(cr, 298.15 K) of p-
terphenyl is equal to 27.5 kJ mol−1 [86], while ΔlcrHAi(Tm) is 35.3 kJ mol−
1
[112]. Using ΔsolnHAi/C6H6(cr, 298.15 K) as an estimate of ΔlcrHAi(298.15
K), one can conclude that the thermal adjustment value should be calcu-
lated assuming a linear behavior of CAp i(l,T) below Tm.
In the works [65,66] we used the available data on the heat capaci-
ties of PAHs, heteroaromatic compounds and their derivatives in solid
R 298:15
and molten states to calculate the T m ½C Ap i ðl; TÞ−C Ap i ðcr; TÞdT values,
assuming linear temperature dependence of CAp i(l, T). CAp i(l, T) and CAp i
(cr, T) functions were fitted to literature data points according to the
method of least squares. Further we calculated their ΔlcrHAi(298.15
K) values according to Eq. (2).
On the other hand, we calculated ΔlcrHAi(298.15 K) of these com-
pounds from the solution enthalpies. In the case of PAHs we accepted
that ΔsolnHAi/C6H6(l, 298.15 K)= 0. In the case of substituted PAHs and
heteroaromatic compounds we used ΔsolnHAi/C6H6(l, 298.15 K) of struc-
turally similar aromatic compounds that are the liquids under standard
conditions. For example, we accepted that solution enthalpies of
dimethylnaphthalenes in the hypothetical liquid state are equal to
ΔsolnHAi/C6H6(l, 298.15 K) of 1,6-dimethylnaphthalene. Such proposal is
confirmed by the fact that isomeric xylenes have nearly equal values
of ΔsolnHAi/C6H6(l, 298.15 K): 0.9 kJ mol−1 for o-xylene, 1.1 kJ mol−1 for
m-xylene and 0.8 kJ mol−1 for p-xylene [65]. Despite the correction as-
sociated with the solution enthalpy of hypothetical liquid is small, it
 M.I. Yagofarov et al. / Journal of Molecular Liquids 256 (2018) 58–66 63

Fig. 3. Heat capacities of (a) o-terphenyl and (b) p-terphenyl as functions of temperature. Black curves – solid state heat capacities; solid red curves – liquid state heat capacities; dashed red
curve – p-terphenyl liquid state heat capacity extrapolated down to 298.15 K assuming its linear temperature dependence; dashed green curve – p-terphenyl liquid state heat capacity
extrapolated down to 298.15 K assuming its quadratic temperature dependence. (For interpretation of the references to colour in this figure legend, the reader is referred to the web ver-
sion of this article.)

should be taken in mind that it has a positive sign, so ΔlcrHAi(298.15
K) estimated only from ΔsolnHAi/C6H6(cr, 298.15 K) can be slightly
(within the limits of 2 kJ mol−1 [65]) overestimated.
ΔlcrHAi(298.15 K) obtained in different ways are provided in Table 3
[65,66].
For the sake of comparison, in column 5 we provide the fusion en-
thalpies adjusted to 298.15 K according to Chickos et al. scheme [54].
This scheme is used by researchers in phase transitions thermochemistry
for adjustment of fusion, vaporization and sublimation enthalpies to
298.15 K [114,115]. According to the scheme, ΔlcrHAi(298.15 K) = ΔlcrHAi
(Tm) – ΔlcrCApi ∙ (Tm – 298.15 K), where ΔlcrCApi is calculated as follows [108]:
 
−1
Δlcr C Ap i = J K−1 mol ¼ 9:83 þ 0:26  C Ap i ðl; 298:15 KÞ−0:15
 C Ap i ðcr; 298:15 KÞ
The values of CAp i(l, 298.15 K) and CAp i(cr, 298.15 K) can be taken from
literature or calculated according to an additive scheme [116].
It can be seen that in most cases the values in columns 3, 4 and 5
agree within the limits of 2 kJ mol−1. Additionally, in most cases thermal
adjustment magnitude is less than 3–4 kJ mol−1.
Average of deviations between columns 3 and 4 is 0.4 kJ mol−1; that
between columns 4 and 5 is 1.0 kJ mol−1. Average of deviations be-
tween columns 3 and 5 is 1.4 kJ mol−1. The values in column 5 are
slightly underestimated on average compared with columns 3 and 4.
The main contribution to the slight disagreement comes from pyrene,
anthracene, and perylene. ΔlcrHAi(298.15 K) values of these compounds
obtained by Chickos et al. scheme are significantly smaller than those
obtained using Kirchhoff's law or solution calorimetry. The reasons of
such differences can be seen in Table 4 containing the ΔlcrCAp i calculated
ð17Þ
as the mean difference of CAp i(l, T) and CAp i(cr, T) functions between

Table 3
Compilation of the fusion enthalpies at the melting temperature and adjusted to 298.15 K in different ways.

Compound ΔlcrHAi(Tm)a ΔlcrHAi(298.15 K) (Eq. 1)b ΔlcrHAi(298.15 K) (Eq. 2)c ΔlcrHAi(298.15 K) (Chickos et al.)d
kJ mol−1 kJ mol−1 kJ mol−1 kJ mol−1

1 2 3 4 5

Naphthalene 19.1 ± 0.1 (353.4) 17.7 17.9 17.0

2-Methylnaphthalene 12.1 ± 0.1 (307.7) 11.8 11.9 11.7
Acenaphthene 21.5 ± 0.1 (366.6) 20.8 19.8 18.7
Fluorene 19.6 ± 0.1 (387.9) 19.1 17.3 15.6
Biphenyl 18.6 ± 0.1 (342.1) 18.2 16.6 16.6
o-Terphenyl 17.2 ± 0.1 (329.4) 15.2 14.4 15.2
7,8-Benzoquinoline 14.1 ± 0.1 (324.1) 12.0 12.9 12.9
Pyrene 17.4 ± 0.1 (423.8) 16.3 14.7 11.4
1,8-Dimethylnaphthalene 17.1 ± 2.0 (337.2) 14.9 17.3 15.6
2,6-Dimethylnapthalene 25.2 ± 0.2 (384.3) 22.5 22.1 20.9
2,7-Dimethylnapthalene 23.6 ± 1.6 (369.0) 21.4 20.8 19.8
Benzophenone 18.4 ± 0.2 (321.2) 16.7 17.6 17.2
E-Azobenzene 22.7 ± 0.3 (341.1) 22.2 21.1 20.7
Diphenylacetylene 21.0 ± 0.7 (334.5) 18.2 19.3 19.3
Dibenzofuran 19.4 ± 0.7 (355.2) 16.6 17.5 17.0
Dimethyl isophthalate 27.8 ± 2.5 (341.1) 23.3 25.7 25.5
1,4-Di-tert-butylbenzene 22.5 ± 0.1 (350.8) 23.2 21.8 19.7
Anthracene 29.4 ± 0.1 (488.9) 24.7 24.8 20.0
p-Terphenyl 35.4 ± 0.1 (478.0) 27.5 27.7 25.1
Dibenzothiophene 21.8 ± 0.4 (371.8) 20.2 18.5 18.5
Triphenylmethane 20.7 ± 0.4 (367.2) 17.0 15.7 16.1
Thianthrene 27.6 ± 0.1 (429.6) 22.4 21.3 21.0
Phenazine 24.9 ± 0.1 (447.9) 20.0 17.4 17.4
Phenanthridine 22.8 ± 0.1 (379.7) 19.4 18.4 18.8
Dimethyl terephthalate 33.7 ± 1.8 (414.3) 27.5 26.4 27.5
Perylene 31.9 ± 0.1 (551.0) 25.3 24.0 17.8
a
The fusion enthalpies at the melting temperatures.
b
The fusion enthalpies values at 298.15 K calculated from Eq. (7) using solution calorimetry.
c
The fusion enthalpies values at 298.15 K calculated from ΔlcrHAi(Tm) (column 2) according to Kirchhoff's law (Eq. 3) assuming that CAp i(l,T) temperature dependence below Tm is linear.
d
The fusion enthalpies values at 298.15 K calculated from ΔlcrHAi(Tm) (column 2) according to Chickos et al. scheme [54].
64 M.I. Yagofarov et al. / Journal of Molecular Liquids 256 (2018) 58–66
Table 4
R Tm
Comparison between the ΔlcrCApi values calculated according to Eq. (17) and as
(cr, 298.15 K).
Compound CAp i(l, 298.15 K)
J K−1 mol−1
Fluorene 250.7 [117]
Biphenyl 250.9 [118]
2,6-Dimethylnaphthalene 247.7 [117]
2,7-Dimethylnaphthalene 251.9 [119]
Dibenzothiophene 250.0 [120]
298.15 K and Tm and by Eq. (17). The heat capacities of liquids at
298.15 K necessary for application of Eq. (17) were calculated by linear
extrapolation of the literature heat capacities of the melt.
Despite the compounds in Table 4 have similar CAp i(l, 298.15 K) and
CAp i(cr, 298.15 K), the mean ΔlcrCAp i values between 298.15 K and Tm are
significantly distinct, while the ΔlcrCAp i values calculated according to
Eq. (17) are nearly equal. The differences are related to the different
slopes of CAp i(l, T) and CAp i(cr, T) temperature dependencies and melting
temperatures.
4. Conclusions
Summarizing, investigations in the field of solution and sublimation
thermodynamics of aromatic compounds lead to following conclusions.
Aromatic compounds are conventionally divided into three groups
depending on the magnitude of deviations among their solution en-
thalpies in benzene at 298.15 K and the corresponding fusion enthalpies
at the melting temperature.
Firstly, it is observed that for a large number of aromatic compounds
not capable of self-association ΔlcrHAi(Tm) and ΔsolnHAi/C6H6(cr, 298.15
K) are approximately equal.
Secondly, the ΔsolnHAi/C6H6(cr, 298.15 K) values of self-associated ar-
omatic compounds notably exceed ΔlcrHAi(Tm). The difference between
ΔsolnHAi/C6H6(cr, 298.15 K) and ΔlcrHAi(Tm) for such compounds is only
weakly influenced by insertion of the substituents, which do not cause
self-association.
Thirdly, for several aromatic compounds not capable of self-
association we found that their ΔsolnHAi/C6H6(cr,298.15 K) values are vis-
ibly smaller than the values of ΔlcrHAi(Tm).
The general relation between ΔlcrHAi(Tm) and ΔsolnHAi/C6H6(cr,298.15
K) of aromatic compounds includes thermal adjustment of the fusion
enthalpy to 298.15 K. Hence, the ΔlcrHAi(Tm) and ΔsolnHAi/C6H6(cr,
298.15 K) values may be used for determination of the fusion enthalpy
temperature dependence. Analysis of the fusion and solution enthalpies
of a set of aromatic compounds for which the literature data on liquid
(CAp i(l, T)) and solid (CAp i(cr, T)) phases heat capacities are available has
shown that CAp i(l, T) between 298.15 K and Tm appear to be linear exten-
sions of CAp i(l, T) above Tm.
Acknowledgements
This work has been performed according to Grant No. 14.
Y26.31.0019 from Ministry of Education and Science of Russian
Federation.
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